EP3310462B1 - Catalyseur de réduction catalytique sélective insensible au surdosage de nh3 - Google Patents

Catalyseur de réduction catalytique sélective insensible au surdosage de nh3 Download PDF

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Publication number
EP3310462B1
EP3310462B1 EP16736947.9A EP16736947A EP3310462B1 EP 3310462 B1 EP3310462 B1 EP 3310462B1 EP 16736947 A EP16736947 A EP 16736947A EP 3310462 B1 EP3310462 B1 EP 3310462B1
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Prior art keywords
scr catalyst
catalyst
support
coating
scr
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EP16736947.9A
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German (de)
English (en)
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EP3310462A1 (fr
Inventor
Joseph Fedeyko
Jing Lu
Hai-Ying Chen
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Johnson Matthey PLC
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Johnson Matthey PLC
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/58—Ammonia
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    • B01D2255/902—Multilayered catalyst
    • B01D2255/9022—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/911—NH3-storage component incorporated in the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/406—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/06—Ceramic, e.g. monoliths
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • F01N2370/04—Zeolitic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/14—Nitrogen oxides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/18—Ammonia
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the invention relates to catalysts for selective catalytic reduction (SCR), articles containing SCR catalysts and methods of using such articles to reduce nitrogen oxides (NO x ).
  • SCR selective catalytic reduction
  • NO x nitrogen oxides
  • NOx nitrogen oxides
  • NO 2 nitrogen dioxide
  • the present invention relates to a method of converting nitrogen oxides in a gas, such as an exhaust gas of a vehicular lean-burn internal combustion engine, to nitrogen by contacting the nitrogen oxides with a nitrogenous reducing agent in the presence of a catalyst comprising a blend of platinum on a support with low ammonia storage with a first SCR catalyst.
  • SCR Selective catalytic reduction
  • nitrogenous compounds such as ammonia or urea
  • SCR technology was first used in thermal power plants in Japan in the late 1970s, and has seen widespread application in Europe since the mid-1980s.
  • SCR systems were introduced for gas turbines in the 1990s and have been used more recently in coal-fired power plants.
  • SCR applications include plant and refinery heaters and boilers in the chemical processing industry, furnaces, coke ovens, municipal waste plants and incinerators.
  • NO x reduction systems based on SCR technology are being developed for a number of vehicular (mobile) applications in Europe, Japan, and the USA, e.g. for treating diesel exhaust gas.
  • reaction (1) 4NO + 4NH 3 + O 2 ⁇ 4N 2 + 6H 2 O (1)
  • reaction (2) Competing, non-selective reactions with oxygen can produce secondary emissions or may unproductively consume ammonia.
  • One such non-selective reaction is the complete oxidation of ammonia, shown in reaction (2). 4NH 3 + 5O 2 ⁇ 4NO + 6H 2 O (2)
  • reaction (3) 4NH 3 + 5NO + 3O 2 ⁇ 4N 2 O + 6H 2 O (3)
  • a catalyst system includes an upstream zone effective to catalyze the conversion of a mixture of NO x and NH 3 to N 2 , and a downstream zone effective for the conversion of ammonia to N 2 in the presence or absence of NOx.
  • a method for preparing a catalyst system includes: first coating one end of a substrate along at least 5% of its length with an undercoat washcoat layer containing a material composition effective to catalyze the removal of ammonia; second coating with an overcoat layer containing a material composition effective to catalyze the conversion of a mixture of NO x and NH 3 to N 2 .
  • a method for treating the exhaust gas stream includes injecting ammonia or an ammonia precursor into an exhaust gas stream of a vehicle, passing the engine exhaust gas stream containing NOx and NH 3 through the upstream zone of a catalyst system to remove NOx and then passing the exhaust gas stream through the downstream zone of the catalyst system to remove NH 3 , as well as other oxidizable species such as hydrocarbons and CO.
  • a catalyst system includes a first zone to abate nitrogen oxides by selective catalytic reduction, a second zone to oxidize ammonia and a third zone to oxidize carbon monoxide and hydrocarbons. Methods for treating the exhaust gas stream are also provided. Methods of making and using such catalysts and catalytic articles are also described.
  • EP2692437 describes an ammonia oxidation catalyst being superior in heat resistance and capable of suppressing by-production of N 2 O or NOx , and leakage of ammonia, by spray supplying urea water or the like to a selective catalytic reduction, in purification of nitrogen oxides discharged from a boiler or the like; and an exhaust gas purification apparatus and an exhaust gas purification method using the same.
  • an ammonia oxidation catalyst or the like for oxidizing and removing surplus ammonia, in selectively reducing nitrogen oxides by adding urea or ammonia and using a selective catalytic reduction (SCR) catalyst, into exhaust gas
  • the ammonia oxidation catalyst is made by coating at least two catalyst layers having a catalyst layer (lower layer) including a catalyst supported a noble metal on an inorganic base material including any of a composite oxide (A) having at least titania and silica as main components, alumina, and a composite oxide (B) consisting of alumina and silica; and a catalyst layer (upper layer) including a composite oxide (C) consisting of at least silica, tungsten oxide, ceria and zirconia, at the surface of an integral structure-type substrate, wherein a composition of the composite oxide (C) is silica: 20% by weight or less, tungsten oxide: 1 to 50% by weight, ceria: 1 to 60% by weight,
  • US 2010/196221 describes an exhaust gas purification catalyst equipment, and a method of use thereof, formed by arranging a selective catalytic reduction type catalyst for purifying nitrogen oxides in exhaust gas exhausted from lean combustion engines using ammonia or urea as a reducing agent, it is provided with a selective catalytic reduction type catalyst, characterized in that said catalyst comprises a lower-layer catalyst layer (A) having an oxidative function for nitrogen monoxide (NO) in exhaust gas and an upper-layer catalyst layer (B) having an adsorbing function for ammonia on the surface of a monolithic structure type carrier (C), and that the lower-layer catalyst layer (A) comprises a noble metal component (i), an inorganic base material constituent (ii) and zeolite (iii), and the upper-layer catalyst layer (B) comprises substantially none of component (i); but the component (iii), in a flow path of exhaust gas, characterized in that a spraying means to supply an urea aqueous solution or an aqueous ammoni
  • the invention relates to a catalytic article comprising a substrate having an inlet and outlet and coated with a first coating comprising a blend of platinum on a support with low ammonia storage with a first SCR catalyst; a second coating comprising a second SCR catalyst; wherein the second coating at least partially overlaps the first coating, and wherein the first SCR catalyst is a Cu-SCR catalyst or a Fe-SCR catalyst, wherein the support with low ammonia storage is a siliceous support comprising a zeolite with silica-to-alumina ratio of ⁇ 100; and wherein the support with low ammonia storage is a support that stores less than 0.001 mmol NH 3 per m 3 of support.
  • the invention is a method of treating exhaust gas comprising NH 3 and NOx, the method comprising contacting an exhaust gas comprising ammonia with a catalytic article as hereinbefore defined.
  • ammonia slip means the amount of unreacted ammonia that passes through the SCR catalyst.
  • a support with low ammonia storage means a support that stores less than 0.001 mmol NH 3 per m 3 of support.
  • the support with low ammonia storage is preferably a molecular sieve or zeolite having a framework type selected from the group consisting of AEI, ANA, ATS, BEA, CDO, CFI, CHA, CON, DDR, ERI, FAU, FER, GON, IFR, IFW, IFY, IHW, IMF, IRN, IRY, ISV, ITE, ITG, ITN, ITR, ITW, IWR, IWS, IWV, IWW, JOZ, LTA, LTF, MEL, MEP, MFI, MRE, MSE, MTF, MTN, MTT, MTW, MVY, MWW, NON, NSI, RRO, RSN, RTE, RTH, RUT, RWR, SEW, SFE, SFF, SFG, SFH, SFN,
  • the molecular sieve or zeolite has a framework type selected from the group consisting of BEA, CDO, CON, FAU, MEL, MFI and MWW, even more preferably the framework type is selected from the group consisting of BEA and MFI.
  • calcine means heating the material in air or oxygen. This definition is consistent with the IUPAC definition of calcination.
  • IUPAC Compendium of Chemical Terminology, 2nd ed. (the “Gold Book”). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997 ). XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8.
  • Calcination is performed to decompose a metal salt and promote the exchange of metal ions within the catalyst and also to adhere the catalyst to a substrate.
  • the temperatures used in calcination depend upon the components in the material to be calcined and generally are between about 300°C to about 900 °C for approximately 1 to 8 hours. In some cases, calcination can be performed up to a temperature of about 1200 °C. In applications involving the processes described herein, calcinations are generally performed at temperatures from about 400°C to about 700 °C for approximately 1 to 8 hours, preferably at temperatures from about 400°C to about 650 °C for approximately 1 to 4 hours.
  • the term "about” means approximately and refers to a range that is optionally ⁇ 25%, preferably ⁇ 10%, more preferably, ⁇ 5%, or most preferably ⁇ 1% of the value with which the term is associated.
  • N 2 selectivity means the per cent conversion of ammonia into nitrogen.
  • a catalyst article comprises a combination of platinum on a support with low ammonia storage and a first SCR catalyst.
  • the combination of platinum on a support with low ammonia storage and a first SCR catalyst is a blend of platinum on a support with low ammonia storage with a first SCR catalyst.
  • the support with low ammonia storage is a siliceous support, where the siliceous support comprises a zeolite with silica-to-alumina ratio of at least one of: ⁇ 100, ⁇ 200, ⁇ 250, ⁇ 300, ⁇ 400, ⁇ 500, ⁇ 750, and ⁇ 1000.
  • the first SCR catalyst is a Cu-SCR catalyst or a Fe-SCR catalyst, more preferably a Cu-SCR catalyst.
  • the ratio of the amount of first SCR catalyst to the amount of platinum on a support with low ammonia storage in the blend can be in the range of 3:1 to 300:1, inclusive, based on the weight of these components.
  • the ratio of the amount of first SCR catalyst to the amount of platinum on a support with low ammonia storage in the blend is in the range of 7:1 to 100:1, inclusive, based on the weight of these components.
  • the ratio of the amount of first SCR catalyst to the amount of platinum on a support with low ammonia storage in the blend is in the range of 10:1 to 50:1, inclusive, based on the weight of these components.
  • active component loading refers to the weight of the support of platinum + the weight of platinum + the weight of the first SCR catalyst in the blend.
  • Platinum can be present in the catalyst in an active component loading from about 0.01 to about 0.25 wt. %, inclusive.
  • platinum can be present in the catalyst in an active component loading from 0.04-0.2 wt. %, inclusive. More preferably, platinum can be present in the catalyst in an active component loading from 0.07-0.17 wt. %, inclusive. Most preferably, platinum can be present in the catalyst in an active component loading from 0.05-0.15 wt. %, inclusive.
  • the compositions can comprise two or three SCR catalysts.
  • the first SCR catalyst which is always present in the compositions, is present in a blend with Pt on a support with low ammonia storage.
  • the first SCR catalyst is a Cu-SCR catalyst or a Fe-SCR catalyst, more preferably a Cu-SCR catalyst.
  • the Cu-SCR catalyst comprises copper and a molecular sieve.
  • the Fe-SCR catalyst comprises iron and a molecular sieve. Molecular sieves are further described below.
  • the copper or iron can be located within the framework of the molecular sieve and/or in extra-framework (exchangeable) sites within the molecular sieve.
  • the second and third SCR catalysts can be the same or different.
  • the second and third SCR catalyst can be an oxide of a base metal, a molecular sieve, a metal exchanged molecular sieve or a mixture thereof.
  • the base metal can be selected from the group consisting of vanadium (V), molybdenum (Mo) and tungsten (W), chromium (Cr), cerium (Ce), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu), and mixtures thereof.
  • compositions consisting of vanadium supported on a refractory metal oxide such as alumina, silica, zirconia, titania, ceria and combinations thereof are well known and widely used commercially in mobile applications. Typical compositions are described in U.S. Pat. Nos. 4,010,238 and 4.085,193 . Compositions used commercially, especially in mobile applications, comprise TiO 2 on to which WO 3 and V 2 O 5 have been dispersed at concentrations ranging from 5 to 20 wt. % and 0.5 to 6 wt. %, respectively.
  • the second SCR catalyst can comprise promoted-Ce-Zr or promoted-MnO 2 . These catalysts may contain other inorganic materials such as SiO 2 and ZrO 2 acting as binders and promoters.
  • the catalyst article can further comprise at least one base metal promoter.
  • a “promoter” is understood to mean a substance that when added into a catalyst, increases the activity of the catalyst.
  • the base metal promoter can be in the form of a metal, an oxide of the metal, or a mixture thereof.
  • the at least one base metal catalyst promoter may be selected from neodymium (Nd), barium (Ba), cerium (Ce), lanthanum (La), praseodymium (Pr), magnesium (Mg), calcium (Ca), manganese (Mn), zinc (Zn), niobium (Nb), zirconium (Zr), molybdenum (Mo), tin (Sn), tantalum (Ta), strontium (Sr) and oxides thereof.
  • the at least one base metal catalyst promoter can preferably be MnO 2 , Mn 2 O 3 , Fe 2 O 3 , SnO 2 , CuO, CoO, CeO 2 and mixtures thereof.
  • the at least one base metal catalyst promoter may be added to the catalyst in the form of a salt in an aqueous solution, such as a nitrate or an acetate.
  • the at least one base metal catalyst promoter and at least one base metal catalyst, e.g., copper, may be impregnated from an aqueous solution onto the oxide support material(s), may be added into a washcoat comprising the oxide support material(s), or may be impregnated into a support previously coated with the washcoat.
  • the SCR catalyst can comprise a molecular sieve or a metal exchanged molecular sieve.
  • molecular sieve is understood to mean a metastable material containing pores of a precise and uniform size that may be used as an adsorbent for gases or liquids. The molecules which are small enough to pass through the pores are adsorbed while the larger molecules are not.
  • the molecular sieve can be a zeolitic molecular sieve, a non-zeolitic molecular sieve, or a mixture thereof.
  • a zeolitic molecular sieve is a microporous aluminosilicate having any one of the framework structures listed in the Database of Zeolite Structures published by the International Zeolite Association (IZA).
  • the framework structures include, but are not limited to those of the CHA, FAU, BEA, MFI, MOR types.
  • Non-limiting examples of zeolites having these structures include chabazite, faujasite, zeolite Y, ultrastable zeolite Y, beta zeolite, mordenite, silicalite, zeolite X, and ZSM-5.
  • Aluminosilicate zeolites can have a silica/alumina molar ratio (SAR) defined as SiO 2 /Al 2 O 3 ) from at least about 5, preferably at least about 20, with useful ranges of from about 10 to 200.
  • SAR silica/alumina molar ratio
  • any of the SCR catalysts can comprise a small pore, a medium pore or a large pore molecular sieve, or combinations thereof.
  • a "small pore molecular sieve” is a molecular sieve containing a maximum ring size of 8 tetrahedral atoms.
  • a “medium pore molecular sieve” is a molecular sieve containing a maximum ring size of 10 tetrahedral atoms.
  • a "large pore molecular sieve” is a molecular sieve having a maximum ring size of 12 tetrahedral atoms.
  • the second and/or third SCR catalysts can comprise a small pore molecular sieve selected from the group consisting of aluminosilicate molecular sieves, metal-substituted aluminosilicate molecular sieves, aluminophosphate (AlPO) molecular sieves, metal-substituted aluminophosphate (MeAlPO) molecular sieves, silico-aluminophosphate (SAPO) molecular sieves, and metal substituted silico-aluminophosphate (MeAPSO) molecular sieves, and mixtures thereof.
  • aluminosilicate molecular sieves selected from the group consisting of aluminosilicate molecular sieves, metal-substituted aluminosilicate molecular sieves, aluminophosphate (AlPO) molecular sieves, metal-substituted aluminophosphate
  • any of the SCR catalysts can comprise a small pore molecular sieve selected from the group of Framework Types consisting of ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SFW, SIV, THO, TSC, UEI, UFI, VNI, YUG, and ZON, and mixtures and/or intergrowths thereof.
  • the small pore molecular sieve is selected from the group of Framework Types consisting of CHA, LEV, AEI, AFX, ERI, SFW, KFI, DDR and ITE.
  • any of the SCR catalysts can comprise a medium pore molecular sieve selected from the group of Framework Types consisting of AEL, AFO, AHT, BOF, BOZ, CGF, CGS, CHI, DAC, EUO, FER, HEU, IMF, ITH, ITR, JRY, JSR, JST, LAU, LOV, MEL, MFI, MFS, MRE, MTT, MVY, MWW, NAB, NAT, NES, OBW, PAR, PCR, PON, PUN, RRO, RSN, SFF, SFG, STF, STI, STT, STW, SVR, SZR, TER, TON, TUN, UOS, VSV, WEI, and WEN, and mixtures and/or intergrowths thereof.
  • the medium pore molecular sieve selected from the group of Framework Types consisting of MFI, FER and STT.
  • any of the SCR catalysts can comprise a large pore molecular sieve selected from the group of Framework Types consisting of AFI, AFR, AFS, AFY, ASV, ATO, ATS, BEA, BEC, BOG, BPH, BSV, CAN, CON, CZP, DFO, EMT, EON, EZT, FAU, GME, GON, IFR, ISV, ITG, IWR, IWS, IWV, IWW, JSR, LTF, LTL, MAZ, MEI, MOR, MOZ, MSE, MTW, NPO, OFF, OKO, OSI, RON, RWY, SAF, SAO, SBE, SBS, SBT, SEW, SFE, SFO, SFS, SFV, SOF, SOS, STO, SSF, SSY, USI, UWY, and VET, and mixtures and/or intergrowths thereof.
  • the large pore molecular sieve is selected from the group of
  • a metal exchanged molecular sieve can have at least one metal from one of the groups VB, VIB, VIIB, VIIIB, IB, or IIB of the periodic table deposited onto extra-framework sites on the external surface or within the channels, cavities, or cages of the molecular sieves.
  • Metals may be in one of several forms, including, but not limited to, zero valent metal atoms or clusters, isolated cations, mononuclear or polynuclear oxycations, or as extended metal oxides.
  • the metals can be iron, copper, and mixtures or combinations thereof.
  • the metal can be combined with the zeolite using a mixture or a solution of the metal precursor in a suitable solvent.
  • metal precursor means any compound or complex that can be dispersed on the zeolite to give a catalytically-active metal component.
  • the solvent is water due to both economics and environmental aspects of using other solvents.
  • suitable complexes or compounds include, but are not limited to, anhydrous and hydrated copper sulfate, copper nitrate, copper acetate, copper acetylacetonate, copper oxide, copper hydroxide, and salts of copper ammines (e.g. [Cu(NH 3 ) 4 ] 2+ ).
  • the molecular sieve can be added to the solution of the metal component to form a suspension, which is then allowed to react so that the metal component is distributed on the zeolite.
  • the metal can be distributed in the pore channels as well as on the outer surface of the molecular sieve.
  • the metal can be distributed in ionic form or as a metal oxide.
  • copper may be distributed as copper (II) ions, copper (I) ions, or as copper oxide.
  • the molecular sieve containing the metal can be separated from the liquid phase of the suspension, washed, and dried. The resulting metal-containing molecular sieve can then be calcined to fix the metal in the molecular sieve.
  • the second and third catalysts comprise a Cu-SCR, and Fe-SCR, vanadium, promoted Ce-Zr or promoted MnO 2 .
  • a metal exchanged molecular sieve can contain in the range of about 0.10% and about 10% by weight of a group VB, VIB, VIIB, VIIIB, IB, or IIB metal located on extra framework sites on the external surface or within the channels, cavities, or cages of the molecular sieve.
  • the extra framework metal can be present in an amount of in the range of about 0.2% and about 5% by weight.
  • the metal exchanged molecular sieve can be a copper (Cu) supported small pore molecular sieve having from about 0.1 to about 20.0 wt. % copper of the total weight of the catalyst. More preferably copper is present from about 0.5 wt. % to about 15 wt. % of the total weight of the catalyst. Most preferably copper is present from about 1 wt. % to about 9 wt. % of the total weight of the catalyst.
  • Cu copper
  • the blend of platinum on a support with low ammonia storage with a first SCR catalyst can further comprise at least one of palladium (Pd), gold (Au) silver (Ag), ruthenium (Ru) or rhodium (Rh).
  • the substrate for the catalyst may be any material typically used for preparing automotive catalysts that comprises a flow-through or filter structure, such as a honeycomb structure, an extruded support, a metallic substrate, or a SCRF.
  • the substrate has a plurality of fine, parallel gas flow passages extending from an inlet to an outlet face of the substrate, such that passages are open to fluid flow.
  • Such monolithic carriers may contain up to about 109 or more flow passages (or "cells”) per square centimeter of cross section (700 or more flow passages (or "cells”) per square inch of cross section), although far fewer may be used.
  • the carrier may have from about about 1 to 93, more usually from about 16 to 93, cells per square centimeter (7 to 600, more usually from about 100 to 600, cells per square inch (“cpsi”)).
  • the passages which are essentially straight paths from their fluid inlet to their fluid outlet, are defined by walls onto which the SCR catalyst is coated as a "washcoat" so that the gases flowing through the passages contact the catalytic material.
  • the flow passages of the monolithic substrate are thin-walled channels which can be of any suitable cross-sectional shape such as trapezoidal, rectangular, square, triangular, sinusoidal, hexagonal, oval, circular, etc.
  • the invention is not limited to a particular substrate type, material, or geometry.
  • Ceramic substrates may be made of any suitable refractory material, such as cordierite, cordierite-a alumina, ⁇ -alumina, silicon carbide, silicon nitride, zirconia, mullite, spodumene, alumina-silica magnesia, zirconium silicate, sillimanite, magnesium silicates, zircon, petalite, aluminosilicates and mixtures thereof.
  • suitable refractory material such as cordierite, cordierite-a alumina, ⁇ -alumina, silicon carbide, silicon nitride, zirconia, mullite, spodumene, alumina-silica magnesia, zirconium silicate, sillimanite, magnesium silicates, zircon, petalite, aluminosilicates and mixtures thereof.
  • Wall flow substrates may also be formed of ceramic fiber composite materials, such as those formed from cordierite and silicon carbide. Such materials are able to withstand the environment, particularly high temperatures, encountered in treating the exhaust streams.
  • the substrates can be a high porosity substrate.
  • high porosity substrate refers to a substrate having a porosity of between about 40% and about 80%.
  • the high porosity substrate can have a porosity preferably of at least about 45%, more preferably of at least about 50%.
  • the high porosity substrate can have a porosity preferably of less than about 75%, more preferably of less than about 70%.
  • porosity refers to the total porosity, preferably as measured with mercury porosimetry.
  • the substrate can be cordierite, a high porosity cordierite, a metallic substrate, an extruded SCR, a filter or an SCRF.
  • a washcoat comprising a blend of platinum on a support with low NH 3 storage and a first SCR catalyst, where the first SCR catalyst is a Cu-SCR catalyst or an Fe-SCR catalyst, can be applied to the inlet side of the substrate using a method known in the art. After application of the washcoat, the composition can be dried and calcined. The second SCR catalyst can be applied in a separate washcoat to a calcined article having the bottom layer, as described above. After the second washcoat is applied, it can be dried and calcined as performed for the first layer.
  • the substrate with the platinum containing layer can be dried and calcined at a temperature within the range of 300°C to 1200°C, preferably 400°C to 700°C and more preferably 450°C to 650°C.
  • the calcination is preferably done under dry conditions, but it can also be performed hydrothermally, i.e., in the presence of some moisture content. Calcination can be performed for a time of between about 30 minutes and about 4 hours, preferably between about 30 minutes and about 2 hours, more preferably between about 30 minutes and about 1 hour.
  • an exhaust system comprising (1) a catalytic article comprising a substrate; a first coating comprising a blend of platinum on a support with low ammonia storage with a first SCR catalyst; a second coating comprising a second SCR catalyst; an inlet and an outlet, where the first coating is positioned on the substrate, the first SCR catalyst is a Cu-SCR catalyst or a Fe-SCR catalyst and the second coating at least partially overlaps the first coating and (2) a means for converting NH 3 and NOx in the exhaust gas.
  • the exhaust system can have an ANR >1.0 for at least a portion of the operating time of the system.
  • the exhaust system can further comprise a third SCR catalyst that provides ⁇ 100% NOx conversion, where the third SCR catalyst is a Cu-zeolite only SCR catalyst and the third catalyst is placed an exhaust gas flow upstream of the catalyst article comprising a substrate; a first coating comprising a blend of platinum on a support with low ammonia storage with a first SCR catalyst; a second coating comprising a second SCR catalyst; an inlet and an outlet, where the first coating is positioned on the substrate, the first SCR catalyst is a Cu-SCR catalyst or a Fe-SCR catalyst and the second coating at least partially overlaps the first coating.
  • the second SCR catalyst can comprise promoted-Ce-Zr or promoted-MnO 2 .
  • an exhaust system comprising (1) a catalytic article comprising a substrate, a first coating comprising a blend of platinum on a support with low ammonia storage with a first SCR catalyst; a second coating comprising a second SCR catalyst; an inlet and an outlet, where the first coating is positioned on the substrate, the first SCR catalyst is a Cu-SCR catalyst or a Fe-SCR catalyst and the second coating overlaps at least 20% of the length of the first coating along a axis from the inlet to the outlet and (2) a means for converting NH 3 and NOx in the exhaust gas.
  • the exhaust system can have an ANR >1.0 for at least a portion of the operating time of the system.
  • the exhaust system can further comprise a third SCR catalyst that provides ⁇ 100% NOx conversion, where the third SCR catalyst is a Cu-zeolite only SCR catalyst and the third catalyst is placed an exhaust gas flow upstream of the catalyst article comprising a substrate; a first coating comprising a blend of platinum on a support with low ammonia storage with a first SCR catalyst; a second coating comprising a second SCR catalyst; an inlet and an outlet, where the first coating is positioned on the substrate, the first SCR catalyst is a Cu-SCR catalyst or a Fe-SCR catalyst and the second coating at least partially overlaps the first coating.
  • the second SCR catalyst can comprise promoted-Ce-Zr or promoted-MnO 2 .
  • a method of improving the N 2 yield from ammonia in an exhaust gas at a temperature from about 200 °C to about 350 °C comprises contacting an exhaust gas comprising ammonia with a catalytic article comprising a substrate; a first coating comprising a blend of platinum on a support with low ammonia storage with a first SCR catalyst; a second coating comprising a second SCR catalyst; an inlet and an outlet, where the first coating is positioned on the substrate, the first SCR catalyst is a Cu-SCR catalyst or a Fe-SCR catalyst and the second coating at least partially overlaps the first coating.
  • the improvement in yield can be about 10% to about 20% compared to a catalyst comprising a comparable formulation in which the first SCR catalyst is present as a first layer and supported platinum is present in a second layer and gas comprising NH 3 and NO passes through the first layer before passing through the second layer.
  • a method of reducing N 2 O formation from NH 3 and NOx in an exhaust gas comprises contacting an exhaust gas comprising ammonia with a catalytic article comprising a substrate; a first coating comprising a blend of platinum on a support with low ammonia storage with a first SCR catalyst; a second coating comprising a second SCR catalyst; an inlet and an outlet, where the first coating is positioned on the substrate, the first SCR catalyst is a Cu-SCR catalyst or a Fe-SCR catalyst and the second coating at least partially overlaps the first coating.
  • the reduction in N 2 O formation can be about 20% to about 80% compared to a catalyst comprising a comparable formulation in which the first SCR catalyst is present as a first layer and the supported platinum is present in a second layer and gas comprising NH 3 and NO passes through the first layer before passing through the second layer.
  • Another aspect of the invention relates to a method of treating exhaust gas comprising NH 3 and NO x with a catalytic article according to claim 1.
  • a bi-layer formulation having a Pt on alumina bottom layer and a SCR top layer was used as a comparative example.
  • a bottom layer was applied to a ceramic substrate using a washcoat comprising 0.3wt. % Pt on alumina.
  • the washcoat was applied to a ceramic substrate, and then the washcoat was pulled down the substrate using a vacuum.
  • the article was dried and calcined at about 500 °C for about 1 hour.
  • the loading of Pt on the article was 106 g/m 3 (3 g/ft 3 ).
  • a top layer was applied to the substrate coated with the bottom layer using a second washcoat comprising a Cu-CHA, and then the washcoat was pulled down the substrate using a vacuum.
  • the article was dried and calcined at about 500 °C for about 1 hour.
  • the loading of Cu-CHA in the top layer was 0.110 g/cm 3 (1.8 g/in 3 ).
  • This material is Example 1.
  • An aged sample was prepared by aging a sample of Example 1 for 50 hours at 620 °C in an atmosphere containing 10% H 2 O.
  • a bi-layer formulation having a Pt on alumina bottom layer and a SCR top layer was used as a comparative example.
  • a bottom layer was applied to a ceramic substrate using a washcoat comprising 0.17 wt. % Pt on a blend of alumina and bare zeolite.
  • the washcoat was applied to a ceramic substrate, and then the washcoat was pulled down the substrate using a vacuum.
  • the article was dried and calcined at about 500 °C for about 1 hour.
  • the loading of Pt on the article was 106 g/m 3 (3 g/ft 3 ).
  • a top layer was applied to the substrate coated with the bottom layer using a second washcoat comprising a Cu-CHA, and then the washcoat was pulled down the substrate using a vacuum.
  • the article was dried and calcined at about 500 °C for about 1 hour.
  • the loading of Cu-CHA in the top layer was 0.165 g/cm 3 (2.7 g/in 3 ).
  • This material is Example 2.
  • An aged sample was prepared by aging a sample of Example 2 for 50 hours at 620 °C in an atmosphere containing 10% H 2 O.
  • the washcoat was applied to a ceramic substrate, and then the washcoat was pulled down the substrate using a vacuum.
  • the article was dried and calcined at about 500 °C for about 1 hour.
  • the loading of Pt, the zeolite and the Cu-CHA on the article was 106 g/m 3 (3 g/ft 3 ), 0.011 g/cm 3 (0.18 g/in 3 ), and 0.110 g/cm 3 (1.8 g/in 3 ), respectively.
  • a top layer was applied to the substrate coated with the bottom layer using a second washcoat comprising a Cu-CHA, and then the washcoat was pulled down the substrate to a distance of about 50% of the length of the substrate using a vacuum.
  • the article was dried and calcined at about 500 °C for about 1 hour.
  • the loading of Cu-CHA in the top layer was 0.110 g/cm 3 (1.8 g/in 3 ).
  • the article was cut at an appropriate location along the length of the article to form a new smaller article having 100% of the blend bottom layer covered by the Cu-CHA top layer.
  • This material is Example 3.
  • An aged sample was prepared by aging a sample of Example 3 for 50 hours at 620 °C in an atmosphere containing 10% H 2 O.
  • the washcoat was applied to a ceramic substrate, and then the washcoat was pulled down the substrate using a vacuum.
  • the article was dried and calcined at about 500 °C for about 1 hour.
  • the loading of Pt, the zeolite and the Cu-CHA on the article was 106 g/m 3 (3 g/ft 3 ), 0.0055 g/cm 3 (0.09 g/in 3 ), and 0.055 g/cm 3 (0.9 g/in 3 ), respectively.
  • a top layer was applied to the substrate coated with the bottom layer using a second washcoat comprising a Cu-CHA, and then the washcoat was pulled down the substrate to a distance of about 50% of the length of the substrate using a vacuum.
  • the article was dried and calcined at about 500 °C for about 1 hour.
  • the loading of Cu-CHA in the top layer was 0.110 g/cm 3 (1.8 g/in 3 ).
  • the article was cut at an appropriate location along the length of the article to form a new smaller article having 100% of the blend bottom layer covered by the Cu-CHA top layer.
  • This material is Example 4.
  • An aged sample was prepared by aging a sample of Example 4 for 50 hours at 620 °C in an atmosphere containing 10% H 2 O.
  • the washcoat was applied to a ceramic substrate, and then the washcoat was pulled down the substrate using a vacuum.
  • the article was dried and calcined at about 500 °C for about 1 hour.
  • the loading of Pt, the zeolite and the Cu-CHA on the article was 106 g/m 3 (3 g/ft 3 ), 0.00275 g/cm 3 (0.045 g/in 3 ), and 0.055 g/cm 3 (0.9 g/in 3 ), respectively.
  • a top layer was applied to the substrate coated with the bottom layer using a second washcoat comprising a Cu-CHA, and then the washcoat was pulled down the substrate to a distance of about 50% of the length of the substrate using a vacuum.
  • the article was dried and calcined at about 500 °C for about 1 hour.
  • the loading of Cu-CHA in the top layer was 0.110 g/cm 3 (1.8 g/in 3 ).
  • the article was cut at an appropriate location along the length of the article to form a new smaller article having 100% of the blend bottom layer covered by the Cu-CHA top layer.
  • This material is Example 5.
  • An aged sample was prepared by aging a sample of Example 5 for 50 hours at 620 °C in an atmosphere containing 10% H 2 O.
  • Examples 3, 4 and 5 significantly reduced N 2 O formation, with up to an 85% N 2 O reduction between 200 and 300 °C. NO conversion and N 2 yield is also significantly higher in Examples 3, 4 and 5.
  • SCR reaction on Cu is promoted and unselective NH 3 + NO reaction on Pt (with the primary product being N 2 O) and parasitic NH 3 oxidation on Pt (which reduces available NH 3 for SCR reaction on Cu) are minimized.
  • Examples 2, 4 and 5 contained the same amount of Cu-SCR catalysts, N 2 O formation was much lower and NO conversion was much higher in Example 4 and 5.
  • ANRs a mmonia to N O r atio
  • Increasing the ANR from 1.0 to 1.4 improves NO conversion in all catalysts, suggesting that an ANR > 1 is desirable for optimal NOx removal efficiency.
  • At a high ANR of 1.4 i.e. not enough NO to react with all the NH 3 resulting in NH 3 slip from the Cu-SCR component
  • all three catalysts testes showed almost no NH 3 slip at 250 °C or above. This is expected because of the presence of Pt in all three catalysts that is highly active for NH 3 oxidation.
  • Examples 3 and 5 demonstrate that the Cu-catalyzed SCR reaction is promoted and the Pt-catalyzed unselective NO + NH 3 reaction is minimized when both NOx and NH 3 are present in the feed.
  • Figure 3 shows the NO + NH 3 reaction performance on systems with a Cu-SCR catalyst with various volume in the upstream and Examples 1 and 5 in downstream of the Cu-SCR.

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Claims (12)

  1. Article catalytique comprenant un substrat présentant une entrée et une sortie et revêtu d'un premier revêtement, comprenant un mélange de platine sur un support doté d'un faible stockage d'ammoniac et d'un premier catalyseur SCR ; un deuxième revêtement comprenant un deuxième catalyseur SCR ; le deuxième revêtement recouvrant au moins partiellement le premier revêtement et le premier catalyseur SCR étant un catalyseur Cu-SCR ou un catalyseur Fe-SCR, le support doté d'un faible stockage d'ammoniac étant un support silicié comprenant une zéolithe dotée d'un rapport silice-à-alumine ≥100 ; et
    le support doté d'un faible stockage d'ammoniac étant un support qui stocke moins que 0,001 mmole de NH3 par m3 de support.
  2. Article catalytique selon la revendication 1, le deuxième revêtement recouvrant complètement le premier revêtement.
  3. Article catalytique selon la revendication 1, le support doté d'un faible stockage d'ammoniac étant un support silicié comprenant une zéolithe dotée d'un rapport silice-à-alumine ≥ 1000.
  4. Catalyseur selon la revendication 1, le mélange comprenant du platine sur un support doté d'un faible stockage d'ammoniac comprenant en outre au moins l'un parmi le palladium (Pd), l'or (Au), l'argent (Ag), le ruthénium (Ru) ou le rhodium (Rh).
  5. Article catalytique selon la revendication 1, le premier catalyseur SCR comprenant du Cu ou du Fe chargé sur un tamis moléculaire choisi dans le groupe de types de structure constitué par ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SIV, THO, TSC, UEI, UFI, VNI, YUG, ZON, BEA, MFI et FER et des mélanges et/ou des intercroissances correspondants.
  6. Article catalytique selon la revendication 1, le deuxième catalyseur SCR étant un métal de base supporté sur un tamis moléculaire, le métal de base étant choisi dans le groupe constitué par le vanadium (V), le molybdène (Mo) et le tungstène (W), le chrome (Cr), le cérium (Ce), le manganèse (Mn), le fer (Fe), le cobalt (Co), le nickel (Ni) et le cuivre (Cu) et les mélanges correspondants.
  7. Article catalytique selon la revendication 1, le substrat étant de la cordiérite, une cordiérite à porosité élevée, un substrat métallique, un nid d'abeille extrudé ou un filtre.
  8. Article catalytique selon la revendication 1, le deuxième catalyseur SCR étant situé sur le côté entrée du catalyseur comprenant le mélange de platine sur un support doté d'un faible stockage d'ammoniac avec le premier catalyseur SCR.
  9. Article catalytique selon la revendication 1, le deuxième catalyseur SCR étant situé sur le côté sortie du catalyseur comprenant le mélange de platine sur un support doté d'un faible stockage d'ammoniac avec le premier catalyseur SCR.
  10. Article catalytique selon la revendication 1, le deuxième catalyseur SCR comprenant du Ce-Zr dopé ou du MnO2 dopé.
  11. Article catalytique selon l'une quelconque des revendications 1, 3, 4, 5, 6, 7, 8, 9 et 10, le deuxième revêtement recouvrant au moins 20% de la longueur du premier revêtement le long d'un axe allant de l'entrée vers la sortie.
  12. Procédé de traitement d'un gaz d'échappement comprenant de l'ammoniac et du NOx, le procédé comprenant la mise en contact d'un gaz d'échappement comprenant de l'ammoniac avec un article catalytique selon la revendication 1.
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EP3310462A1 (fr) 2018-04-25
GB2541500A (en) 2017-02-22
GB201610521D0 (en) 2016-08-03
JP6830451B2 (ja) 2021-02-17
CN107847862A (zh) 2018-03-27
GB2541500B (en) 2019-06-26
US10322372B2 (en) 2019-06-18
JP2018526194A (ja) 2018-09-13
KR102527239B1 (ko) 2023-05-02
US20190299160A1 (en) 2019-10-03
KR20180034400A (ko) 2018-04-04
US9878287B2 (en) 2018-01-30
WO2016205441A1 (fr) 2016-12-22
RU2018101694A3 (fr) 2019-07-24
DE102016111000A1 (de) 2016-12-22
US20160367937A1 (en) 2016-12-22
RU2018101694A (ru) 2019-07-19
CN107847862B (zh) 2020-12-18
US20180147530A1 (en) 2018-05-31
RU2715539C2 (ru) 2020-02-28

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